Durable antistatic agent, hydrophobic fibers and fibrous structures having durable antistatic property and method of making same

ABSTRACT

A novel antistatic agent soluble in organic solvent which can afford durable antistatic property to hydrophobic fibers and fibrous structures is provided. Such antistatic agent consists substantially of a complex compound of a polyvinyl derivative having quaternary ammonium groups in its side chains, its counter anion being substituted with an anionic surfactant containing 2 to 8 ethylene oxide units, an esterbonded sulfonate, an alkylamidocarboxylic acid salt or an amphoteric surfactant of carboxylic acid type. Hydrophobic fibers and fibrous structures having durable antistatic property, and a process for producing such hydrophobic fibers and fibrous structures also are provided, by utilizing the above antistatic agent.

United StatesPatent 91 Ogata et al.

[451 Feb. 4, 1975 DURABLE ANTISTATIC AGENT,

HYDROPHOBIC FIBERS AND FIBROUS STRUCTURES HAVING DURABLE ANTISTATIC PROPERTY AND METHOD OF MAKING SAME [75] Inventors: Yuzuro Ogata, Wakayama; Yukihisa Niimi, Osaka,both of Japan [73] Assignees: Kao Soap Co., Ltd.; Kanebo, Ltd.,

both of Tokyo, Japan [22] Filed: Aug. 30, 1972 [21] App]. No.: 284,863

[30] Foreign Application Priority Data Sept. 1, 1971 Japan 46-67297 [52] US. Cl....260/79.3 M, 260/85.5 ES, 260/86.1 N 260/86.7, 260/89.5 N, 260/DlG. 18

[51] Int. Cl C08f 3/92, C08f 15/36, C08f 3/62 [58] Field of Search 260/89.5 N, 79.3 M, 85.5 ES, 260/86.1 N, 86.7, DIG. 18

[56] References Cited UNITED STATES PATENTS 3,178,397 4/1965 Olaj et a1. 260/DIG. 18

3,361,718 1/1968 Fujimoto 3,661,880 5/1972 Markert et al....' 260/89.5 N

FOREIGN PATENTS OR APPLICATIONS 2,009,478 0/1969 Germany 260/D1G. 18

Primary Examiner-Morris Liebman Assistant Examiner-S. L. Fox

Attorney, Agent, or Firm-Woodhams, Blanchard and Flynn [57] ABSTRACT Hydrophobic fibers and fibrous structures having durable antistatic property, and a process for producing such hydrophobic fibers and fibrous structures also are provided, by utilizing the above antistatic agent.

10 Claims, No Drawings DURABLE ANTISTATIC AGENT, HYDROPI'IOBIC FIBERS AND FIBROUS STRUCTURES HAVING DURABLE ANTISTATIC PROPERTY AND METHOD OF MAKING SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel antistatic agent soluble in organic solvent which can afford durable antistatic property, highly resistant to washing and dry cleaning, to hydrophobic fibers made of such polymers as polyester, polyacrylic, polyamide, polyvinylchloride, polyethylene and polypropylene polymers as well as fibrous structures such as cloth and knit fabrics made of such fibers, if applied to those fibers of fibrous structures in an organic solvent system.

Further, the present invention relates to hydrophobic fibers and fibrous structures having durable antistatic property and a method for producing such fibers and fibrous structures.

2. Description of the Prior Art Hydrophobic fibers and fibrous structures made of such fibers as mentioned above have excellent properties such as toughness and chemical resistance, but, as they are hydrophobic, they have great volume specific resistance and, therefore. they tend to produce a remarkable static electrification phenomenon even by a slight friction, thus causing various electrostatic faults.

Such faults will not only hinder a normal operation of the process steps for producing textile goods from textile fibers, for example, drawing and twisting, winding, warping, knitting and weaving, sewing, etc., but also cause lowering of product qualities or various troubles such as stains on products due to dust absorption and unpleasant feelings to human bodies.

There have been proposed various methods for preventing electrostatic faults of hydrophobic fibers and fibrous structures made of such fibers. There are known methods of adding a material having antistatic property to a fiber-forming polymer substance so as to make it copolymerize or blend with the polymer substance (for example, refer to Japanese Patent Publication No. 24l43/l97l) and methods of attaching a material having antistatic property on fibers or fibrous structures (for example, refer to Japanese Patent Publication No. 9849/1964, Japanese Patent Publication No. 22920/l97l and U.S. Pat. No. 2,729,577).

However, the former method has disadvantages such as the low dispersibility of the antistatic agent is liable to cause breaking of yarns and occurence of knotted yarns during melt spinning or lowering of qualities such as reduction of strength and elasticity. Further, due to thermal deterioration caused in melt spinning, dispersion into the coagulating bath in wet spinning, etc., only special kinds of antistatic agent can be used.

On the other hand, the latter method is a temporary antistatic treatment method, in which, since the antistatic agent is stripped off by washing, the antistatic effect is gradually lowered or completely lost, which has not only the disadvantage of hurting the feeling of fibrous structures, but also has a greater disadvantage of not having a durable antistatic effect.

Further, in conventional methods for antistatic treatment offibrous structures, many of them use emulsions of antistatic agents added with emulsifiers, which lack in durability such as mentioned above. Therefore, they do not provide a durable antistatic effect. Further. among those conventional antistatic agents which have been utilized in an aqueous medium or system, those having relatively low HLB values could be utilized in a solvent system. because they are solvent soluble, but they have been insufficient with respect to their durabilities.

Recently. methods for treating hydrophobic fibrous structures by using an organic solvent as medium which is superior to a conventional method of treatment wherein water is used as medium have attracted attention because of their efficiency and economical advantage and also because of the fact that enviornmental pollution by waste water has posed a social problem.

' However, effective and durable antistatic agents which can be used in an organic solvent system cannot be found among conventional antistatic agents.

SUMMARY OF THE INVENTION We have made extensive researches for obtaining hydrophobic fibers and fibrous structures which show excellent durable antistatic property and-have excellent hand, and accomplished the present invention.

In the specification and claims, the words fibrous structure" means staple fibers, continuous filaments, woven fabrics, knitted fabrics, non-woven fabrics, battings and the like.

The primary object of the present invention is to provide an antistatic agent which is soluble in an organic solvent to form a stable solution and which has a high resistance against washing and dry cleaning when applied to hydrophobic fibers or fibrous structures.

Another object of the present invention is to provide fibers and fibrous structures having durable antistatic property and also having excellent hand.

Another object of the present invention is to provide a process for producing fibers and fibrous structures having durable antistatic property and also having excellent hand easily on an industrial scale and economically.

The above objects of the invention can be attained by using, as the durable antistatic agent to be used in an organic Solvent medium or system, a complex compound consisting of a polyvinyl derivative having a quaternary ammonium group in its side chain and having a counter anion derived from a particular anionic surfactant or an amphoteric surfactant as defined below.

In case a fibrous structure is treated with a cationic polymer as an antistatic agent, it is generally apt to be given a hard hand feeling. However, when the antistatic agents according to the present invention are used, a desirable soft hand can be imparted to the textile material. This is one of characteristic features of the invention.

The durable antistatic agent for solvent system of the present invention comprises a complex compound consisting of a polyvinyl derivative having a quaternary ammonium group in its side chain, the counter anion thereof being substituted with at least one surface active compound selected from the group consisting of anionic surfactants containing 2 8 ethylene oxide units, ester-bonded sulfonates, alkylamidocarboxylic acid salts amphoteric surfactants of the carboxylic acid type.

Further, the present invention provides hydrophobic fibers and fibrous structures having durable antistatic property which contain 0.1 to l()% by weight ofa com- 3 plex compound consisting ofa polyvinyl derivative having a quaternary ammonium group in its side chain, the counter anion thereof being substituted with at least one surface active compound selected from the group 1 consisting of anionic surfactants containing 2 8 ethylene oxide units, esterbonded sulfonates. alkylamidocarboxylic acid salts and amphoteric surfactants of the carboxylic acid type.

Also, the process of the present invention comprises treating a hydrophobic fibrous structure with an organic solvent solution consisting of 0.05 to 10% by weight of a complex compound consisting of a polyvinyl derivative having a quaternary ammonium group in its side chain, the counter anion thereof being substituted with at least one surface active compound selected from the group consisting of anionic surfactants containing 2 8 ethylene oxide units, esterbonded sulfonates, alkylamidocarboxylic acid salts and amphoteric surfactants of the carboxylic acid type, 0.05 to by weight of alcohols and more than 70% by weight of at least one organic solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, ketones and esters, the weight ratio of said alcohols to said complex compound being more than 0.2/1.

The polyvinyl derivatives having quarternary ammonium groups in their side chains to be used in the present invention are those obtained by, for example, the following processes:

1. A process which comprises homopolymerizing a vinyl monomer having at least one tertiary amine residue in the molecule or copolymerizing the same with another copolymerizable vinyl monomer and then quaternizing the resulting polymer by a suitable quaternizing agent, or

2. A process which comprises homopolymerizing a vinyl monomer having at least one quaternary ammonium group in the molecule or copolymerizing the same with another copolymerizable vinyl monomer. The vinyl monomers having at least one tertiary amine residue in the molecule are those represented by the general formula:

/ca 3 c cooca ca N The vinyl monomers having at least one quaternary ammonium group in the molecule are those represented by the general formula:

coocn ca n a x wherein R and R,-, are vinyl residues. and preferably R, represents hydrogen or methyl and R represents an alkoxycarbonyl group. alkoxy group. CONH- COOH, -CN or C H Particularly preferred copolymerizable vinyl monomers are acrylic acid. acrylic esters, acrylonitrile. styrene and acrylamides.

In the above process (1), conventional quaternizing agents such as dimethylsulfate, diethylsulfate. methyl halides and ethyl halides may be used for. the quaternization of the tertiary amines.

The molar ratio of the vinyl monomer having a tertiary amine residue or vinyl monomer containing quaternary ammonium group to the other copolymerizable vinyl monomer is properly 1:0-1.

The complex compound of the present invention comprises the above polyvinyl derivative containing quaternary ammonium groups in its side chains, but the counter anion thereof being substituted with a particular anionic surfactant or amphoteric surfactant.

As'such particular anionic surfactants, there may be used at least one anionic surfactant selected from the group consisting of anionic surfactants containing 2 8 ethylene oxide units (preferably 3 5 ethylene oxide units), esterbonded sulfonates and alkylamidocarboxylic acid salts.

Further, such particular amphoteric surfactants are those of carboxylic acid type.

As examples of those surfactants, there may be mentioned the following compounds: Sodium dioxyethylene dodecyl ether sulfate, sodium trioxyethylene dodecyl ether sulfate, sodium trioxyethylene-n-nonylphenyl ether sulfate, sodium pentaoxyethylene dodecyl ether sulfate, sodium octaoxyethylene-n-nonylphenyl ether sulfate, sodium trioxyethylenedodecyl ether monophosphate, sodium trioxyethylene-n-nonylphenyl ether monophosphate, sodium trioxyethylenedodecyl ether carboxymethylate, sodium trioxyethylene-nnonylphenyl ether carboxymethylate, sodium trioxyethylene-n-nonylphenyl ether B-carboxy ethylate, sodium dioctylsuccinate monosulfate, N-methyl-N- (sodium carboxymethyl)lauroamide, sodium N- lauroylglutamate, sodium 2-carboxyethyldodecylamine, sodium carboxymethyldodecylamine, di(sodium carboxymethyl)dodecylamine and di(sodium 2- carboxymethoxyethyl)dodecylamine.

The antistatic agent of the present invention, that is to say, the complex compound as mentioned above, is applied to the textile material (textiles or fabrics) in an amount of 0.1 to 10% by weight, preferably 0.2 to 3% by,weight, most preferably 0.3 to 1.0% by weight. When the attached amount is less than 0.1% by weight, the antistatic effect is still insufficient, while. when it exceeds 10% by weight, the hand or feeling of the finished textile material is remarkably lowered, though the antistatic effect is improved.

The hydrophobic fibers to be treated in the present invention include polyesters, polyacrylonitrile, polyamides, polyvinyl chloride, polyethylene and polypropyrene, but polyesters and polyacrylonitrile are preferable. Further, the fibrous structures (woven, knitted, etc.) to be treated in the present invention mean staple fibers. continuous filaments, clothes, woven goods, knitted goods, non-woven clothes, battings, etc. which should contain more than 50% by weight of said hydrophobic textiles.

The application of the antistatic agent (complex compound) to the fibers or fibrous structures to be treated should be carried out by utilizing an organic solvent as the medium.

The concentration of the complex compound in the organic solvent solution should be in the range of 0.05 to by weight, preferably 0.2 to 3.0% by weight. Particularly, 0.3 to 1.0% by weight is most preferable. 1n case the antistatic agent concentration is less than 0.05% by weight, it is impossible to put a required amount of the complex compound on the textile material uniformly and, further, the production efficiency is lowered. On the other hand, when it exceeds 10% by weight, the uniform application of the antistatic agent becomes impossible owing to the increase of the solution viscosity and adhesive substances (socalled gum) will be adhered to the machinery and the textile fabrics, and product qualities and workability will be remarkably lowered.

As the alcohols to be used in the present invention, methyl alcohol, ethyl alcohol, isopropyl alcohol, nbutyl alcohol, isoamyl alcohol, n-octyl alcohol, benzyl alcohol, o-chlorophenol, m-cresol, n-hexyl alcohol are exemplified. Ethyl alcohol and isopropyl alcohol are particularly suitable. The amount of alcohols in the organic solvent solution should be in the range of 0.05 to by weight, preferably 0.2 to 6% by weight, most preferably 0.3 to 2% by weight. Further, the amount of alcohols should be at least 0.2 part by weight based on 1 part by weight of the antistatic agent (complex compound), but alcohols should be preferably used in the amount of 0.5 to 30 parts by weight, particularly 1 to 20 parts by weight to 1 part by weight of the complex compound. In case the alcohol concentration is less than 0.05% by weight, the preparation of the antistatic agent solution will be difficult, while, in case it exceeds 20% by weight, deterioration of the product qualities, particularly discoloring of the product, will be caused. Further, if the ratio of the amount of alcohols to the amount of the complex compound is less than 0.2/1, it will be difficult to dissolve the antistatic agent into the solvent solution.

As organic solvents, there can be used hydrocarbons such as n-hexane, cyclohexane, benzene, and toluene; halogenated hydrocarbons such as methyl chloride, methylenechloride, chloroform, carbontetrachloride, methylchloroform, dichloroethane, trichloroethylene, tetrachloroethane, perchloroethylene, dichlorobenzene and trichlorobenzene; ethers such as diethyl ether, methylethylether and ethylpropylether; ketones such as acetone and methylethylketone; esters such as ethyl acetate, methyl acetate and butyl acetate. Halogenated hydrocarbons, particularly methylchloroform, trichloroethylene and perchloroethylene are preferable. The organic solvent should be used in a concentration of at least 70% by weight. but the concentration is preferably in the range of 92 to 99.6% by weight and more preferably in the range of 97 to 99.4% by weight. In case, the concentration of the organic solvent is less than 70% by weight, the alcohol concentration is so much increased that deterioration of product qualities,

particularly ,discloration of the product might be caused. I

l The organic solvent solution of the antistatic agent (i.e., complex compound) can he usually prepared. by swelling and dissolving the complex compound in a predetermined weight ratio of alcohols and then dissolving the obtained solution in the organic solvent.

The organic solvent solution of the complex compound thus obtained can be applied to a fibrous structure by any conventional method such as dipping, padding, coating and spraying. Generally, padding and coating are suitable to woven fabrics, and dipping, spraying and padding are suitable to knitted fabrics. Further, in case offilament and tow, dipping and spraying are suitable.

The amount of said organic solvent solution to be applied to a fibrous structure depends on the concentration of said solution, the kinds of the material to be treated and the amount of the complex compound to be attached, but, for example, in the case of treating a woven fabric by a dipping method, the liquid is squeezed so as to make the solution to be 30 to by weight based on the fabric prior to the treatment by said organic solvent solution, the material to be treated should be preferably washed by said organic solvent, because such pretreatment will assist a uniform adhesion of the antistatic agent and increase the durability of the antistatic property.

The fibrous structure treated by the antistatic agent of the present invention can be used as a final product as it is, but also it can be further subjected to a resin finishing. Further, if the fibrous structure should be treated by a melamine resin, the melamine resin can be simultaneously used with the organic solvent solution of the present invention and, therefore, the omission of a particular resin finishing step is possible. In the case of the simultaneous use of a melamine resin, the durability of the antistatic effect can be increased without lowering the antistatic property.

The process of the present invention can be carried out at room temperature to obtain excellent effects, but, generally, the durability can be further increased by treating a fibrous structure under heat, after the organic solvent solution is applied to the fibrous structure and the solvent is removed therefrom. The temperature of such heat treatment depends on the kinds of the fibrous strusture, but it is generally in the range of 60 to 210C and the treatment is carried out for 10 seconds to 20 minutes. Particularly, the range of 1 10 to 190C is preferable. The heat treatment is carried out, for example, in a temperature of 150 to 200C for polyesters and in a temperature of 1 10 to C for polyacrylonitriles.

The fibrous structures to be treated according to the process of the present invention include yarn dyed goods, piece dyed goods and scoured and bleached goods. Further, the process can be applied to such secondary goods such as sweaters and -jumpers.

1n the process of the present invention, wetting or penetrating agents, stabilizing agent, etc. such as dialkylsulfosuccinates and alkyl phosphates can be preferably used to increase the solution stability of the organic solvent solution. Further, softening agents and other kinds of antistatic agents can be used together, if

necessary.

The fibers or fibrous structures thus obtained have an excellent antistatic effect, particularly, a remarkably 7 improved durability compared to conventionally available products and, therefore, the antistatic effect of the obtained fibers or fibrous structure is not lowered by washing. Further, in case a melmaine resin is used together, the durability of the antistatic effect is further increased, in addition to the resin finishing effect. Also, the color fastness to rubbing is not lowered and the occurence of water spots can be prevented.

The present invention will now be illustrated in more detail by way of Examples.

EXAMPLE 1 Preparation of poly(Z-methacryloyloxyethyldimethylethylammonium ethosulfate) (hereinafter will be referred to as homopolymer A) in a liter four-neck flask provided with a Dimroth condenser, a thermometer, a dropping funnel and a blowing pipe, 1088 g (7 moles) of 2- dimethylaminoethylmethacrylate are charged. Then, 1078 g (7 moles) of diethyl sulfate are added thereto dropwise over about l.5 hours under countrol of generation of heat while temperature should be kept at below 50C. After the exothermic reaction has ceased, the mixture is stirred at 50C for 30 minutes in air to complete the quaternization reaction. Thereafter, 8 1 9l gof water were added thereto to obtain the aqueous solution. After thorough replacement of air in the system with nitrogen gas, a solution of 17.4 g of potassium persulfate in 500 g ofwater is added to the mixture and the whole is allowed to react at 50C for 7 hours under stirring. The conversion was 96.3% and the viscosity of the obtained solution was 368 cp. aqueous solution at 30C).

EXAMPLE 2 continued further at a room temperature for additional 7 30-60 minutes to complete the reaction. The precipitate is collected by filtration under reduced pressure, washed thorougly with water of 2 to 3 times as much as the precipitate several times and dried at 60C under reduced pressure overnight to obtain 39 g of a white solid product (yield 98.3%).

EXAMPLE 3 Preparation of a complex compound from homopolymer A and sodium trioxyethylene-dodecyl ether sulfate To I00 g of 20% aqueous homopolymer A solution, 100 g of sodium trioxyethylene dodecyl ether sulfate aqueous solution) are added dropwise with vigorous stirring. A precipitate is formed as soon as the addition starts. By the same procedures as in Example 2, 36 g of a pale yellowish brown solid product are obtained (yielded 96%).

EXAMPLE 4 Preparation of a complex compound from homopolymer A and sodium pentaoxyethylene-n-nonylphenyl ether mo'nophosphonate To I00 g of 20% aqueous homopolymer A solution. 137 g of sodium pentaoxyethylene-n-nonylphenyl ether monophosphonate (25% aqueous solution) are added dropwise with vigorous stirring. By the same procedures as in Example 2. 40 g ofa white solid product are obtained (yield 89.571).

EXAMPLE 5 Preparation of a complex compound from homopolymer A and sodium dioctylsuccinate sulfonate To l00 g of 20% aqueous homopolymer A solution. 1 l5 g of sodium dioctylsuccinate sulfonate (25% aqueous solution) are added dropwise with vigorous stirring. By the same procedures as in Example 2, 37 g of a light brown resinous solid product are obtained (yield 96.7%).

EXAMPLE 6 Preparation of copolymer of styrene and 2- methacryloyloxyethyldimethylethylammonium ethosulfate (which will be refer to as copolymer B" hereinbelow) In a 2 liter fourneck flask provided with a Dimroth condenser, a thermometer, a dropping funnel and a blowing pipe, l04 g (1 mole) of styrene and 157 g (1 mole) of Z-dimethylaminoethyl methacrylate are dissolved in 559 g ofdioxane. After thorough replacement of air in the system with nitrogen gas, a solution of 1.3 g of azobisisobutylonitrile in 50 g of dioxane is added thereto. After the polymerization reaction at 50C for 10 hours, a solution of 3 g of azobisisobutylonitrile in 50g of dioxane is further added to the mixture and the polymerization is continued at 50C for further l5 hours. After completion of the polymerization, 154 g (1 mole) of diethylsulfate are added to the mixture and the temperature is elevated to C to effect the quaternization reaction. A precipitate occurs immediately and the reaction is continued for further one hour.

After completion of the quaternization reaction, dioxane is distilled off under reduced pressure and the residue is dissolved in water to obtain 2340 g of l7.7% viscous, milky aqueous solution.

EXAMPLE 7 Preparation of a complex compound from the copolymer B obtained in Example 6 and sodium dioctylsuccinate sulfonate To g of l7.7'/r aqueous copolymer B solution. 76 g of 25% aqueous sodium dioctylsuccinate sulfonate solution are added dropwise with vigorous stirring at a room temperature. After completion of the addition, stirring is continued at a room temperature for further l hour to complete the precipitation and the resulting precipitate is gathered by filtration. The filtered precipitate is washed thoroughly with water and dried at 60C under reduced pressure overnight to obtain 27 g of white solid (yield 89.0%).

EXAMPLE 8 Preparation of a complex compound from copolymer B and sodium pentaoxyethylene-nmonylphenyl ether phosphate 5 To I g of l7.7% aqueous copolymer B solution, 91.5 g of 25% aqueous sodium pentaoxyethylene-nnonylphenyl ether phosphate solution are added dropwise with vigorous stirring at room temperature. By the same procedures as in Example 7, 33 g ofa light yellow solid product are obtained (yield 96.5%

EXAMPLE 9 Preparation of a complex compound from copolymer B and sodium trioxyethylene-n-nonylphenyl ether sulfate By adding sodium trioxyethylene-n-nonylphenyl ether sulfate to the aqueous copolymer B solution in the same manner as in Example 7. a light yellow solid product is obtained (yield 98%).

EXAMPLE l0 Preparation of copolymer of acrylonitrile and 2- methacryloyloxyethyldimethylethylammonium ethosulfate (which will be referred to as copolymer C" hereinafter) In a 5 liter flask similar to that used in Example 6. l5) g (3 moles) of acrylonitrile and 311 g (1 mole) of Z-methacryloyloxyethyldimethylethyl ammonium ethosulfate are dissolved in 4073 g of water and air in the reaction system is replaced thoroughly with nitrogen gas. Thereafter, a solution of 4.7 g of potassium persulfate in l00 g of water and successively a solution of 1.8 g of sodium bisulfite in 50 g of water are added to the mixture at 25C and stirring is effected at 25C for 13 hours to complete the polymerization. A part of the thus resulting polymer [degree of polymerization 95%, viscosity of the solution 7.4 cp. aqueous solution at 30C)] is taken, from which water is then removed thoroughly and the nitrogen content in the residue is measured according to the Kjeldahl method. The nitrogen content is 5.69%. From the result, it is supposed that the proportion of acrylonitrile monomer to the quaternary salt monomer in the copolymer is about 0.336 mole to l mole.

EXAMPLE ll Preparation of copolymerof acrylonitrile and 2- methacryloyloxyethyldimethylethylammonium ethosulfate (which will be referred to as "copolymer D" hereinafter) and quaternization of the copolymer D 159 grams (3 moles) of acrylonitrile and 157 g (1 mole) of Z-dimethylaminoethyl methacrylate are dissolved in 2742.4 g of dioxane and air in the reaction system is replaced thoroughly with nitrogen gas. Thereafter. a solution of 0.316 g of azobisisobutylonitrile in dioxane is added'to the mixture and the polymerization is carried out at 50C. A solution of 0.316 g of azobisisobutylonitrile in g of dioxane is added thereto after every 10. 20, and 40 hours. The polymerization is completed after hours. The conversion is 93.6% and ['nl C 0.358. A part of the thus resulting polymer is taken, from which water is then removed thoroughly and the nitrogen content in the residue is measured according to the Kjelkahl method. The nitrogen content is l0.77%. From the result, it is supposed that the proportion of acrylonitrile to Z-dimethylaminoethyl methacrylate in the copolymer is about 0.349 mole to 1 mole.

146 grams of diethylsulfate are added to 3 Kg of the above aqueous polymer solution and the temperature is elevated to C to effect the quaternization. lmmediately, precipitate is formed. The reaction is continued at 80C for l hour.Thereafter, dioxane is distilled off under reduced pressure and the residue is dissolved in water to obtain an aqueous solution of the quaternized copolymer. The viscosity of the solution is ll.3 cp. l()% aqueous solution at 303C).

EXAMPLE l2 Preparation of a complex compound from copolymer C obtained in Example 10 and sodium trioxyethylene dodecyl ether sulfate The quaternary ammonium group of the copolymer C is reacted with an equimolar amount of sodium trioxyethylene dodecyl ether sulfate in the same manner as in Example 3 to obtain a solid product (yield 95%).

EXAMPLE 13 Preparation of a complex compound from copolymer D prepared and quaternized in Example 1 l and sodium trioxyethylene dodecyl ether sulfate The reaction is carried out in the same manner in Example l2 and a solid product is obtained (yield EXAMPLE l4 Preparationof a complex compound from homopolymer A, sodium dioctyl succinate sulfonate and sodium lauryl sulfate In the same manner as in Example l2. sodium dioctyl succinate sulfonate and sodium lauryl sulfate (molar ratio 1:1 are reacted with homopolymer A to obtain a solid product (yield 100%).

EXAMPLE l5 Preparation of a complex compound of homopolymer A and sodium lauryloyl sarcosinate By reacting the starting materials in the same manner as in Example 12. a solid product is obtained (yield EXAMPLE 16 Preparation of a complex compound from homopolymer A, dodecyldimethylaminocarboxymethylbetaine (C H 'N (CH;,) 'CH COO') and sodium lauryl sulfate Homopolymer A is reacted with dodecyldimethylaminocarboxymethylbetaine and sodium lauryl sulfate (molar ratio lzl in the same manner as in Example 12 to obtain a solid product (yield 90% EXAMPLE 17 Preparation of a complex compound from homopolymer A, sodium trioxyethylene dodecyl ether sulfate and potassium n-octylsesquiphosphate Homopolymer A is reacted with sodium trioxyethylene dodecyl ether sulfate and potassium n-octylsesquiphosphate (molar ratio lzl) in the same manner as in Example 12 to obtain a solid produce (yield 93%).

EXAMPLE 18 A complex compound is obtained from homopoly- EXAMPLE I) A complex compound is obtained from homopolymer A and a compound of the following formula in the same manner as in Example l2:

/C CH c Iii-CH ca eu oca CH COONa EXAM PLE A complex compound is obtained in the same manner as in Example 3 except that sodium dioxyethylene dodecyl ether sulfate is used.

EXAMPLE 2l A complex compound is obtained in the same manner as in Example 3 except that sodium octaoxyethylene dodecyl ether sulfate is used. I

REFERENTIAL EXAMPLE I A complex compound is obtained from homopolymer A and sodium laurate in the same manner as in Example 12.

REFERENTIAL EXAMPLE 2 A complex compound is obtained from homopolymer A and lauryl sulfate in the same manner as in Example 12.

Each of the compositions prepared in the above Examples was dissolved in perchloroethylene, trichloroethylene or methylchloroform to obtain a solution of 03% solid content. An aliquot of 100 ml from the solution was placed in a beaker as the treating solution. In the treating solution, sample cloth pieces (20 X 20 cm) of each of fabrics of polyester (tropical: dyed in a dark color), nylon (tricot: not dyed) and acrylic (knitted fabric: not dyed) were immersed at a room temperature for 10 seconds. They were squeezed with a mangle to 120 wt.% liquid, air-dried and subjected to heating at 160C for 2 minutes. The following tests of properties were carried out:

l. Antistatic property:

Five test pieces in round shape (diameter 5 cm) were cut from the treated cloth and allowed to stand at C under 40% RH for 24 hours. Insulating resistance (surface electrical resistivity) of the test pieces was mea- Table sured with a resistance meter (manufactured by Horikawa Denki Col). Average of the five values was taken as the-antistatic property.

2. Resistance to washing (wet method Five test pieces same as in the above item 1 were placed in a container of a laundry tester. which were then added with ml of 02% aqueous solution of a detergent (New Wonderful of Kao Soap Co.. Ltd.). Washing was done at 40C for 20 minutes. The same washing procedure was repeated ten times. Finally, the test pieces were washed twice each with l liter of warm water, dehydrated and dried and the antistatic property was measured in the same manner as in item 1.

3. Resistance to dry cleaning:

Five round test pieces (the same as in item I) were placed in the laundry tester and washed with 100 ml of a perchloroethylene solution containing 1% of a blend of anionic and non-ionic surfactants (Charge Soap P of Kao Soap Co., Ltd.) and 0.1% of water at 30C for 30 minutes. The test pieces were rinsed finally twice each with 100 ml of perchloroethylene.

4. Color fastness to rubbing:

After I00 rubbings with a rubbing tester under a load of 200 g, the results were evaluated according to the specification of JlS-L-l048. As the number is larger, the color fastness is better.

5. Hygroscopicity:

A drop of water was applied on the test piece through a burette and the time (in second) required for penetration was measured.

6. Feeling (Hand):

Mainly softness was judged by handling.

When the untreated sample cloth (blank) is 0 A.

O Softer than blank A A little harder than blank X Harder than blank The test results of the properties of the samples examined according to the above described methods of judgement or measurement were as shown in the following Tables 1 to 3.

T, P and M in the following tables indicate trichloroethylene, perchloroethylene and methylchloroform, respectively. Compounds of the referential examples did not dissolve in a solvent such as perchloroethylene or trichloroethylene to make a stable solution. Further. the compound of Referential Example l was far inferior in the color fastness to rubbing.

One of the ingredients of each of the surfactant mixtures used in Examples l4 and 16 is the complex compound of the present invention, but the other ingredient is not the one according to the present invention. However, by using such a combination, excellent results as shown in the following Tables 1 to 3 can be obtained.

Polyester cloth (made of textured yarn and dyed in a dark color) Solvent Antistatic property (insulating resistance 0) Color Hygro- Example for Before fastness scopicity Feelin No. treatlaundry After laundry (5 times) After laundry (10 times) to rubbing (second) 9 went Wet Dry Wet Dry Wet Dry 'r 8.9xl0 5.5xl0 3.6xl0 6.5xl0 6.8xl0 3 45 16 A o 3 P 7.5xl0 4.2xl0 2.6xl0 8.2xl0 4.1xl0 3-4 4-5 81 A o 4 P 1.3xl0 6.1xl0 2.2x1o 7.9xl0 4.4x10 3 4 54 Table 1 Continued Polyester cloth (made of textured yarn and dyed in a dark color) Solvent Antistatic property (insulating resistance Q) Dolor Hygrobxdwle 50: Before v fa'st-ness scopicity Feeling No. treatlaundry Af ter laundry (5 times) After laundry (10 times) to 'rubbing (second) ment Wet Dry wet Dry wet Dry 5 P 2. 2x10 8.2xl 3.9xl0 1. lxlO 7. 2x10 2-3 4-s 32 A 7 P 1.1xlQ 7.3xl0 3.8x10 8.1xl0 5.5xl0 3-4 4-5 52 A x a T 2.6xl0 4.4x1o 2.6xl0 7. 7x10 5.6x10 4 P 4 2s A 9 'r 3.3xl0 6.2x1o 1.6x1o 4 4 Above 3 mins. A

12 P 1.03:10 9.51m) 2.1x1o 3-4 4 150 A o 13 T 1. x10 1.1x 3. 3x10 4-5 5 5 A o 14 P 2. 5x10 P.1x10 1.6xl0 i 4 4-5 Above 3 mins. 0

15 P 1. 8x10 7.62410 3. 8x10 3 4 15 o 16 '1' 5.5xl0 5. 4x10 1.6x10 2-3 4 Above 3 mins. A

17 7 Pa e.5x1o 3.1xl0 1.9x1o 3-4 4-5 0 A 18 '1 7. 8x10 5. 2x10 3. 4x10 9.33410 3 4 Above 3 mins. 0

19 P 4.5x10 8.72410 4.1x1o 1.0xl0 4 s 31 A 20 P 9.3xl0 5.0xl0 3. 3x10 9.6xl0 3 4-5 93 A O 21 P 2.13m) 6.8xl0 2.3xl0 1.1)(10 3-4 4 45 A Ref. Example 1 M 3. 8x10 4. 3x10 3. 7x10 1. 3xl0 3 2 63 A 8 9 9 9 Example 2 M 4.1xl0 5.5xl0 4.4xl0 9.1xl0 3 4 Above 3 mins. A

Aqueous 8 l0 12 system Water 5.5xl0 5.6xl0 1.5xl0 4 3-4 25 X Blank Above 10 Above 10 Above 10 Above 10 4-5 4 Above 3 mins. A 0

Table 2 Polyacrylic (knitted fabric) Example Solvent for Antistatic property (insulating resistance (l/cm) Feeling No. treatment Before After laundry After laundry (Softness) laundry (5 times) (10 times) (Wet (Wet Dry) 4 Dry) 2 T 142x10" 2.6Xl0'" 3.4 |0'" A 4.2 l()" 4.8xl0" 3 P 6.2Xl0 LSXIO'" 11x10" o A 4 P 53x10 2.6Xl0' x.5 10'" A 5 P 7.6Xl0 3.4 10'" 41 10'" A l.8 l(l 6.6xl0" 7 P 8.4Xl0 94x10" 1.7xl0' A 8 T 9.1 t0 11x10 34x10" A- x 9 T 241x10" 6 l()" 9.| 10"- A- x II P 5.5x) 4 l()' 8.8 l()'" 0- A LZXH)" x10" 13 r iuxlu 241x10 (axio 0 9mm" 3.6Xl0" l4 P |.5 m LXXIU'" klxltl'" A 0 l.5 l(l" 3.7 l0

3,864,317 l5 16 Table 2-Continued I Polyacrylic (l nitted fabric) Example Solvent for Antistatic property (insulating resistance ll/cm) Feeling No. treatment Before After laundry After laundry (softness) laundry (5 times) (10 times) (Wet (Wet Dry) Dry) a is P 9.3Xl QT'I'XIO" 3.2Xl0'" O 2.2Xlt) 58x10" [6 T 5.41m llllXl l' 5.2Xlll'" A ZUXIU flbXltJ I7 P 3X10 SXIO 4.8Xl0'" 7.6Xl0" LZXlO'" Aqueous system Water l.5 l()" 4.0Xl0" 8.5Xl0" X 8.5Xl0 9.2Xl0 Blank IO ll) ll) 0 A Table 3 Nylon (tricot) Example Solvent for Antistatic property (insulating resistance Q/cm) Feeling No. treatment Before After laundry After laundry (softness) laundry times) l0 times) (Wet (Wet Dry) Dry) 2 v T 32x10" 7.4xi0" 9.5 |0" A 3 P Ltxtt)" 8.5Xl0" 55x10 0 4 P 9.6XIO |.2 rsxno A I 35x10 S.2 l() 5 P LSXIO" 8.2xlt)" 8. 1x10" A 0 l.l l0"' 2.l l0

7 P r |.3 |0" 6.5Xl0 80x10 A i l.6 l0' 2.7 |0'" s T l.() l() 4.| |0" 6.7Xl0" A I 8.8x) 8.6Xl0" q T 2.2 |0" X.5 l()" 11x10" A 12 P 8.1x) 4.4 |0" 8.1XIO" 0 73x10" 6.9Xl0

l3 T LIXH)" 2.8Xl0'" 5.1 |0'" 0 6.l l()" l.2Xl() 14 P 31x10" 16x10" 44x10 A-0 6.2Xl0" l.2xl0' P 11x10 x10 6.5Xl0" 0 5.s 10" 9.6Xl0" l6 T 93x10 62x10" 71x10" A l7 P 13x10" 73x10" 83x10" A 0 6.2 10 l.l l()" Aqueous system Water 2.8Xl0" 2.5Xl0 8.4XIO'" X |.2 |0'" 15x10" Blank l0 1 l0 O-A ln the following Examples 22 to 26, various proper- Bath ratio; 1 50 ties of the treated fabrics were measured by the follow- Laundry condition; 40C X 15 minutes and water ing methods: washing for 5 minutes Laundry: The above treatment constitutes one laundry and the Machine; Laundry machine of Toshiba VH-800 same operation is repeated. (Revolutions of 435 rpm) 4 Electrification voltage: Detergent; Heavy Duty detergent (New Wonder- Test pieces of 5 X 7 cm cut from the treated cloth ful" of Kao Soap Co., Ltd.) Concentration 2 g/l were allowed to stand at 20C under 50% RH for 24 hours and electrification voltages of the test pieces were measured by a rotary static tester (of Kyod ai Kaken type and manufactured by Koa Shokai), using cotton calico No. 3 as rubbing cloth and under a load of 500 g and at revolutions of 760 rpm. Average of the four values was taken as the electrification voltage.

Insulating resistance:

Five test pieces in round shape (diameter 5 cm) were cut from the sample cloth and allowed to stand at 20C under 50% RH. Insulating resistances of the test pieces were measured with an electrometer (manufactured by Takeda Riken Co.. Ltd.). Average of the five values was taken.

Feeling (Hand):

Appearance and hand feeling of the sample cloth were judged by a panel of IO persons according to the following standards of judgement and average was taken.

18 the following standardsof judgement:

Nogumup-.. I

Gum upon the mangle Gum up on the 'eloth'" EXAMPLE 22 A polyester tropical (75 d/32 f/2, density of 80 yarns/inch) was dipped in an organic solvent solution having a composition shown in Table 4 at a room temperature and nipped at a squeezing ratio of I007! o.w.f. Then, it was dried at 80C for one minute and heated at 160C for 2 minutes for setting. In Table 4, a complex compound of poly(2-methacryloyloxyethyldimethylethylammonium ethosulfate) and sodium trioxyethylenedodecyl ether sulfate prepared in Example 3 was used. Compositions of treating solutions and test results are summarized in Table 4.

Table 4 Amount Upper column: No. Complex lsopropyl Perchloroof Antistatic Electrification eomalcohol ethylene attached property voltage (V) workabilipound I com- Lower column: ty pound (A owf) Resistance Feeling (gum up) Before After I After'S laundry laundry laundry 8.6Xl0" 4.3Xl0'" 5.l'4 l0" l.2 l0 -3.-l l0' 23X l0'" 7.8Xl0 9.7Xl0 3 [.iiX'lO' 6.6Xl0 9.8Xl0j' 1.2Xl0'" 7 1 l 98.0 l 5 760 .610 3.x 0

4.2Xl0 6.4)( 7.3Xl0

.'Z.5 l0 5.lXl.0" 7.8Xl0

9 5 5 90.0 5 I3 570 720 10 O A 1.2Xl0 4.3Xl0 6.1Xl0

l0 l0 l0 80.0 [0 7 230 450 2.6 A

2.l l0 l.2 l0" 2.1Xl0" ll l5 l5 70.0 ll I 240 1.9 X

9.3Xl0" 5.3 l0" 9.3Xl0

l2 l5 :0 05.0 15 s 70 2.1 x

X.2 l0 3.8Xl0 8.3Xl0" EXAM PLE 23 Vcrv Excellent 5 Excellent 4 A polyester ersey (310 g/yard) was dipped in an org l l' f ganic solvent solution. obtained by dissolving 0.3% by l g mm 1 60 weight of a complex compound in '0.3 by weight of workability (Gum up):

An endless cloth of polyester tropical d/32 f/2) of 40 cm width was padded in the treating solution. nipped under 2 kg/cm and further dried at C. This operation was repeated at a speed of 7 m/min for a period of 30 minutes and the workability was judged by isopropyl alcohol and then diluting it with 99.4% by weight of an organic solvent shown in Table 5. at a room temperature. nipped by'a mangle to a squeezing ratio of I607: and dried at 80C for l .minute.-As the complex compound. a complex compound from copolymer of Z-methacryloyloxyethyldim'ethylethylammonium ethosulfate and acrylamidel .l l and sodium 3,864,317 19 dioctylsuccinate monosulfonate was used. Test results are shown in Table 5.

Further, the electrification voltage of the unfinished polymer of 2-methacryloyloityethylditnethylethylammonium ethosulfate and acrylon itrile (3 2 l) and sodium pentaoxyethylenenonyl phenyl ether sulfate was test piece was 6200 V and its insulating resistance was used. I

more than 2 l (2. In case water was used 'as diluent Test results are shown in Table'6.

Table 6 Test Antistatic Upper column: No. cloth property Electrification voltage (V) Feeling Lower column:

Resistance ((2) non- Before After 1 After 5 finished laundry laundry laundry l Acryl 6.]00 I 2,000 2.425 4.2

tricot 2 82x10 9 .1 10" l.2 l0' 2 Nylon 4,800 230 1.950 2.l50 3.7

tricot 2Xl0 l.l l0" 8.7Xl0" 2.2Xl0

3 TC 3.200 1.280 L450 4.3

broad 8.4 l0 7.5 l0 9,2Xl0 l.2 l0" 4 Cotton 40 I85 780 650 3.2

broad l.3 l0 3.5 l0" 4.4Xl0" 5.3Xl0" instead of an organic solvent. the complex compound 25 EXAMPLE 25 was insoluble in water and, therefore, the test was impossible to be carried out. The solubility in Table 5 was determined by observing the state of the solution by naked eyes after a sufficient agitation and 5 hours standing.

The standards for judgement are as follows:

A dyed cloth of polyester cashmere (warp l d/32 f/l weft 100 d/48 f/l was dipped in an organic solvent solution shown in Table 7 at a room temperature, nipped to a squeezing ratio of 160% o.w.f. and dried at 30 l20C. Test results were shown in Table 7.

The dyeing was made by using Dianix violet SRSE (manufactured by Mitsubishi Kasei Co.. Ltd.) as dye- Dissolved O Dissolved (swollen, A stuff and employing a with temperature and pressure Insoluble X dyeing tester (Colorpet l2 manufactured by Japan Table 5 Upper column:

No. Organic solvent Antistatie Electrification property voltage (V) Solubility Feeling Lower column:

Resistance ((2) Before After l After 5 laundry laundry laundry l Trichloroethylene I 1,800 2.100 O 3.8

8.4)(10 7.2Xl0" l.2 l0" 2 Methylchloroform 1.450 1,700 o 4.1

7.8Xl0 5.2Xl0" -8.3Xl0"' 3 Acetone l20 2,l50 2,350 O 4.2

LZXlO" l.4 l0' 2.5Xl0" 4 Cyelohexane 2.300 2,650 0 3,7

:Ll'lXIO l,0 l0" 4.3X10'" 5 Diethylether I45 L800 2,800 O 3.9

2.5Xl0 9.8Xl0 l.8 l0"' 6 Ethylacetate I80 2.200 2,450 O 3.2

l.2 l0" l.2 l0"' 3.2Xl0'" EXAMPLE 24 Dyeing Machinery Co., Ltd.), ata concentration of 4% o.w.f. and 130C for 60 minutes by a bath ratio of l 30. The reducing washing treatment was conducted by employing the same apparatus as used in the dyeing. in which 2 g/l of hydrosulfite. 2 g/l of soda ash and 2 g/l of Amilazine D (manufactured by Daiichi Kogyo Seiyaku ('o., Ltd.) were used, and the treatment was carried out at C for 30 minutes by a bath ratio of l 50.

The color fading in Table 7 was determined by measuring the absorbance of each organic solvent solution after the treatment at the maximum absorption wavespectrophotometer EPR-Z .(manufactured by Hitachi Seisakusho) and using a cell of I cm size.

What we claim is:

1. An antistatic agent soluble in organic solvents, for imparting a-durable antistatic property to hydrophobic fibers and structures made'therefrom when applied in The solubility was determined by the same method as 5 an organic solvent system; said agent consisting essenin Example 23.

Further, as the complex compound, a complex compound from poly(2-methacryloyloxyethyldimethylethylammonium sulfate) and N-methyl-N- (sodiumcarboxymethyl)-lauroamide was used.

tially of a complex compound of A. poly(2-methacryloyloxyethyltrialkylammonium) cationic polymer. containing from zero to one moles, per mole of 2-methacryoyloxyethyltrialkylammonium units, of units of a second monomer Table 7 Complex Ethyl Perchloro Antistatic Upper column: No. comalcohol ethylene property: Electrification pound voltage (V) Solubility Color fading Lower column: (ahsorhancc) Resistance ((2) Before After I After 5 laundry laundry laundry 5.3Xl0 6.5Xl0" 9.7Xl0

' 6.i'l l0 l*l.7 l0 95x10" 5.9Xl0 7.5Xl0" 9.3 l0

8.3Xl0 8.l 10" 7.5Xl0" X 0.3 84.7 L800 L950 0 0.30

(LI IU 7.1Xl0" ll.7 l0

EXAMPLE 26 having the formula A polyester twill d/32 f/l) was dipped in an or- R ganic solvent solution, obtained by dissolving 0.5% by 40 4 weight ofa complex compound in 0.5% by weight of an CH =C alcohol shown in Table 8 and diluting it with 99% by R weight of perchloroethylene. at a room temperature, nipped to a squeezing ratio of 140% o.w.f. and dried at 100C for 1 minute. Test results are shown in Table 8.

The electrification voltage of the unfinished test cloth was 6800 V and its insulating resistance was more than 2 X 10' Q.

As the complex compound, a complex compound from poly(2-methacryloyloxyethylenedimethylethylammonium sulfate) and sodium trioxyethylene dodecyl ether monophosphate was used.

wherein R is H or methyl. and R,-, is alkoxycarbonyl.

the anions of said polymer having been replaced by.

B. counter anion of at least one surfactant selected from from the group consisting of anionic surfactants containing 2 to '8 ethylene oxide units. esterbonded sulfonates. alkzylamidocarboxylic acid salts and amphoteric surfactants of the carboxylic acid type.

2. An agent as claimed in claim 1, in which the alkyls of said trialkylammonium group, which alkyls can be the same or different, are selected from the group consisting of methyland ethyl.

3. The antistatic agent as claimed in claim Lin which said surfactant is selected from the group consisting of sodium dioxyethylene dodecyl ether sulfate, sodium trioxyethylene dodecyl ether sulfate, sodium trioxyethylene-nnonylphenyl ether sulfate, sodium pentaoxyethylene dodecyl ether sulfate, sodium octaoxyethylene-n-nonylphenyl ether sulfate, sodium trioxyethylenedodecyl ether monophosphate, sodium trioxyethylene-n-nonylphenyl ether monophosphate. sodium trioxyethylenedodecyl ether carboxymethylate. sodium trioxyethylene-n-nonylphenyl ether carboxymethylate and sodium trioxyethylene-n-nonylphenyl ether B-carboxy ethylate.

4. The antistatic agent as claimed in claim 1. in which 23 said surfactant is sodium dioctylsuccinate monosulfonate. i

5. The antistatic agent asclaimed in claim I, in which said surfactant is selected from the group consisting of N-methyl-N-(sodium carboxymethyl) lauroamide and sodium N-lauroylglutamate.

6. The antistatic agent as claimed in claim 1, in which said surfactant is selected from the group consisting of sodium 2-carboxyethyldodecylamine, sodium carboxymethyldodecylamine. di(sodium carboxymethyl)- dodecylamine and di(sodium 2-carboxymethoxyethyl dodecylamine.

7. The antistatic agent as claimed in claim 3, consisting of a complex compound selected from the group consisting of poly( Z-methacryloyloxyethyldimethylethyl ammonium trioxyethylene-n-nonyl phenyl ether sulfate). poly(2-methacryloyloxyethyldimethylethyl ammonium trioxyethylenedodecyl ether sulfate). poly(Z-methacryloyloxyethyldimethylethyl ammonium pentaoxyethylene-n-nonylphenyl ether monophosphonate poly( Z-methacryloyloxyethyldimethylethyl ammonium trioxyethylene-dodecyl ether sulfate), poly(2-methacryloyloxyethyldimethylethyl ammonium dioxyethylenedodecyl ether sulfate). poly(Z- methacryloyloxyethyldimethylethyl ammonium Z-methacryloyloxyethyldimethylethyl methacryloyloxyetliyldimethylethyl ammonium N-lauroyl-N-methyl B-aminopropionate).

10. The antistatic agent as claimed in claim 6, consisting of a complex compound selected from the group consisting of poly( Z-methacryloyloxyethyldimethylethyl ammonium dodecyldimethylaminocarboxymethylbetaine) and poly(2-methacryloyloxyethyldimethylethyl ammonium Z-carboxyethoxyethyl-ldodecylim idazoline 

1. AN ANTISTATIC AGENT SOLUBLE IN ORGANIC SOLVENTS, FOR IMPARTING A DURABLE ANTISTATIC PROPERTY TO HYDROPHOBIC FIBERS AND STRUCTURES MADE THEREFROM WHEN APPLIED IN AN ORGANIC SOLVENT SYSTEM, SAID AGENT CONSISTING ESSENTIALLY OF A COMPLEX COMPOUND OF A. POLY(2-METHACRYLOYLOXYETHYLTRIALKYLAMMONIUM) CATIONIC POLYMER, CONTAINING FROM ZERO TO ONE MOLES, PER MOLE OF 2-METHACRYOYLOXYETHYLTRIALKYLAMMONIUM UNITS, OF UNITS OF A SECOND MONOMER HAVING THE FORMULA
 2. An agent as claimed in claim 1, in which the alkyls of said trialkylammonium group, which alkyls can be the same or different, are selected from the group consisting of methyl and ethyl.
 3. The antistatic agent as claimed in claim 1, in which said surfactant is selected from the group consisting of sodium dioxyethylene dodecyl ether sulfate, sodium trioxyethylene dodecyl ether sulfate, sodium trioxyethylene-n-nonylphenyl ether sulfate, sodium pentaoxyethylene dodecyl ether sulfate, sodium octaoxyethylene-n-nonylphenyl ether sulfate, sodium trioxyethylenedodecyl ether monophosphate, sodium trioxyethylene-n-nonylphenyl ether monophosphate, sodium trioxyethylenedodecyl ether carboxymethylate, sodium trioxyethylene-n-nonylphenyl ether carboxymethylate and sodium trioxyethylene-n-nonylphenyl ether Beta -carboxy ethylate.
 4. The antistatic agent as claimed in claim 1, in which said surfactant is sodium dioctylsuccinate monosulfonate.
 5. The antistatic agent as claimed in claim 1, in which said surfactant is selected from the group consisting of N-methyl-N-(sodium carboxymethyl) lauroamide and sodium N-lauroylglutamate.
 6. The antistatic agent as claimed in claim 1, in which said surfactant is selected from the group consisting of sodium 2-carboxyethyldodecylamine, sodium carboxymethyldodecylamine, di(sodium carboxymethyl)dodecylamine and di(sodium 2-carboxymethoxyethyl)dodecylamine.
 7. The antistatic agent as claimed in claim 3, consisting of a complex compound selected from the group consisting of poly(2-methacryloyloxyethyldimethylethyl ammonium trioxyethylene-n-nonyl phenyl ether sulfate), poly(2-methacryloyloxyethyldimethylethyl ammonium trioxyethylenedodecyl ether sulfate), poly(2-methacryloyloxyethyldimethylethyl ammonium pentaoxyethylene-n-nonylphenyl ether monophosphonate), poly(2-methacryloyloxyethyldimethylethyl ammonium trioxyethylene-dodecyl ether sulfate), poly(2-methacryloyloxyethyldimethylethyl ammonium dioxyethylenedodecyl ether sulfate), poly(2-methacryloyloxyethyldimethylethyl ammonium octaoxyethylene-dodecyl ether sulfate), poly(styrene-2-methacryloyloxyethyldimethylethyl ammonium trioxyethylene-n-nonylphenyl ether sulfate) and poly(acrylonitrile-2-methacryloyloxyethyldimethylethyl ammoniUm trioxyethylene-dodecyl ether sulfate).
 8. The antistatic agent as claimed in claim 4, consisting of a complex compound selected from the group consisting of poly(2-methacryloyloxyethyldimethylethyl ammonium dioctylsuccinate sulfonate) and poly(styrene-2-methacryloyloxyethyldimethylethyl ammonium dioctylsuccinate sulfonate).
 9. The antistatic agent as claimed in claim 5, consisting of a complex compound selected from the group consisting of poly(2-methacryloyloxyethyldimethylethyl ammonium lauroyl sarcosinate and poly(2-methacryloyloxyethyldimethylethyl ammonium N-lauroyl-N-methyl Beta -aminopropionate).
 10. The antistatic agent as claimed in claim 6, consisting of a complex compound selected from the group consisting of poly(2-methacryloyloxyethyldimethylethyl ammonium dodecyldimethylaminocarboxymethylbetaine) and poly(2-methacryloyloxyethyldimethylethyl ammonium 2-carboxyethoxyethyl-1-dodecylimidazoline). 